JP2008184470A - Heavy metal-treating agent excellent in low temperature stability and method for treating heavy metal therewith - Google Patents
Heavy metal-treating agent excellent in low temperature stability and method for treating heavy metal therewith Download PDFInfo
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本発明は、重金属を含有する固体廃棄物、例えば、ゴミ焼却場から排出される焼却灰及び飛灰、重金属に汚染された土壌、排水処理後に生じる汚泥等に含有する鉛、水銀、クロム、カドミウム、亜鉛及び銅等の有害な重金属を簡便に固定化し、不溶出化することを可能にする重金属処理剤に関するものであり、特に高濃度でなおかつ低温において結晶の析出がない低温保存安定性に優れた重金属処理剤に関するものである。 The present invention relates to solid waste containing heavy metals, for example, incineration ash and fly ash discharged from garbage incineration plants, soil contaminated with heavy metals, lead contained in sludge generated after wastewater treatment, mercury, chromium, cadmium It is related to a heavy metal treatment agent that makes it possible to easily fix and elute harmful heavy metals such as zinc and copper, and is particularly excellent in low-temperature storage stability at high concentrations and without crystal precipitation at low temperatures. Heavy metal treating agent.
都市ゴミ焼却工場などから排出される飛灰は重金属含有率が高く、重金属の溶出を抑制する処理を施すことが必要である。その様な処理方法のひとつとして薬剤処理法があり、キレート系薬剤などの重金属処理剤を添加して重金属を処理する方法が用いられている。 Fly ash discharged from municipal waste incineration plants has a high heavy metal content and needs to be treated to prevent elution of heavy metals. As one of such treatment methods, there is a drug treatment method, and a method of treating a heavy metal by adding a heavy metal treatment agent such as a chelate-type drug is used.
キレート系薬剤としてはアミン誘導体のジチオカルバミン酸塩が主に用いられている。特にピペラジンジチオカルバミン酸塩は他のアミン誘導体と比較して硫化水素、二硫化炭素等の有害ガス発生が少ないため、重金属処理剤として広く用いられている。（例えば特許文献１参照）しかしながら、特に高濃度のピペラジンジチオカルバミン酸塩の水溶液は低温における保存安定性が悪く、ジチオカルバミン酸塩の結晶が析出する等の問題があった。 As chelating agents, amine derivatives of dithiocarbamate are mainly used. In particular, piperazine dithiocarbamate is widely used as a heavy metal treating agent because it generates less harmful gases such as hydrogen sulfide and carbon disulfide than other amine derivatives. (For example, refer to Patent Document 1) However, an aqueous solution of piperazine dithiocarbamate having a high concentration has a problem that storage stability at low temperatures is poor and crystals of dithiocarbamate are precipitated.
重金属処理剤の低温安定性を向上させる方法として、重金属処理剤成分にカルボン酸基、スルホン酸基、水酸基、リン酸基、ホスホン酸基およびこれらのアルカリ金属塩からなる群から選ばれる１種以上の官能基を有し、数平均分子量が１０００〜３００００のオリゴマーを添加する方法が提案されている。（例えば特許文献２参照）他にもジエチルジチオカルバミン酸塩においてピペラジン及びポリアミンからなる群から選ばれる１種を０．１から５重量％含有させる方法が提案されている。（例えば特許文献３参照）しかし、これらの方法では低温析出の抑制効果は必ずしも十分でなく、重金属処理剤に添加する添加物が高価であったり、添加後の剤の物性（粘度等）に影響が出る場合があり、さらには製造の工程が増え煩雑となり原単位が悪化する等の問題があった。 One or more types selected from the group consisting of carboxylic acid groups, sulfonic acid groups, hydroxyl groups, phosphoric acid groups, phosphonic acid groups, and alkali metal salts thereof as a method for improving the low temperature stability of the heavy metal treating agent There has been proposed a method of adding an oligomer having a functional group of and a number average molecular weight of 1,000 to 30,000. (For example, refer to Patent Document 2) In addition, a method of containing 0.1 to 5% by weight of one kind selected from the group consisting of piperazine and polyamine in diethyldithiocarbamate has been proposed. (For example, refer to Patent Document 3) However, these methods do not always have a sufficient effect of suppressing low-temperature precipitation, and the additive added to the heavy metal treatment agent is expensive or affects the physical properties (viscosity, etc.) of the agent after the addition. In some cases, the production process becomes complicated and the basic unit deteriorates.
これまでのピペラジンジチオカルバミン酸塩を主成分とする重金属処理剤では、特に高濃度なものでは低温で結晶析出するという安定性の問題があった。本発明は、低温安定性の高い高濃度のピペラジンジチオカルバミン酸塩を主成分とする重金属処理剤を安価かつ簡便に提供することにある。 Conventional heavy metal treating agents mainly composed of piperazine dithiocarbamate have a problem of stability in that crystals are precipitated at a low temperature particularly at high concentrations. An object of the present invention is to provide a heavy metal treating agent having a high concentration of piperazine dithiocarbamate having a high stability at low temperature as a main component at a low cost and in a simple manner.
本発明者等は上記の課題を解決すべく鋭意検討を重ねた結果、高濃度のピペラジンジチオカルバミン酸塩を主成分とする重金属処理剤において、共存するアルカリ水酸化物の含有濃度がある特定の濃度において、低温安定性が著しく高く、なおかつ有害ガスの発生もないことを見出し、本発明を完成するに至ったものである。 As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have a specific concentration in which the concentration of coexisting alkali hydroxide is present in the heavy metal treatment agent mainly composed of a high concentration of piperazine dithiocarbamate. The inventors have found that the stability at low temperatures is remarkably high and no harmful gas is generated, and the present invention has been completed.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の重金属処理剤は、ピペラジンジチオカルバミン酸塩を含んでなる重金属処理剤である。ピペラジンジチオカルバミン酸塩としては、特にピペラジンジチオカルバミン酸塩がピペラジンジ―Ｎ，Ｎ’―ビスカルボジチオ酸塩、さらにはピペラジンジ―Ｎ，Ｎ’―ビスカルボジチオ酸塩がカリウム塩であることが好ましい。カリウム塩では本発明のアルカリ濃度の範囲によって高濃度と低温安定性が両立した重金属処理剤となる。 The heavy metal treating agent of the present invention is a heavy metal treating agent comprising piperazine dithiocarbamate. As piperazine dithiocarbamate, it is particularly preferable that piperazine dithiocarbamate is piperazine di-N, N′-biscarbodithioate, and piperazine di-N, N′-biscarbodithioate is potassium. In the case of the potassium salt, a heavy metal treating agent having both high concentration and low temperature stability is obtained depending on the alkali concentration range of the present invention.
本発明のピペラジンジチオカルバミン酸塩は、ピペラジンジチオカルバミン酸のアルカリ塩を使用できるが、溶解度が高く、熱的に安定なカリウム塩であることが望ましい。 As the piperazine dithiocarbamate of the present invention, an alkali salt of piperazine dithiocarbamate can be used, but it is desirable to be a potassium salt having high solubility and being thermally stable.
本発明のピペラジンジチオカルバミン酸塩を含んでなる重金属処理剤は、主成分のピペラジンジチオカルバミン酸塩がピペラジンジ―Ｎ，Ｎ’―ビスカルボジチオ酸塩であることが好ましいが、本発明の効果を阻害しない範囲でピペラジンジ―Ｎ―カルボジチオ酸塩或いは他のアミン塩を含んでも良い。 In the heavy metal treating agent comprising the piperazine dithiocarbamate of the present invention, the main component piperazine dithiocarbamate is preferably piperazine di-N, N′-biscarbodithioate, but does not inhibit the effects of the present invention. A range of piperazine di-N-carbodithioates or other amine salts may be included.
本発明の重金属処理剤のピペラジンジチオカルバミン酸塩の濃度は３８〜４２％の範囲であり、特に４０〜４２％の範囲が好ましい。３８％未満では、薬剤が低濃度であり単位重量あたりの重金属処理の効率が低く、４２％を越える高濃度では結晶析出を抑えることが難しい。 The concentration of piperazine dithiocarbamate in the heavy metal treating agent of the present invention is in the range of 38 to 42%, and particularly preferably in the range of 40 to 42%. If it is less than 38%, the concentration of the drug is low and the efficiency of heavy metal treatment per unit weight is low, and if it is more than 42%, it is difficult to suppress crystal precipitation.
ピペラジンジ―Ｎ，Ｎ’―ビスカルボジチオ酸塩は、特許文献１他に記載された方法に従い、ピペラジンとアルカリ水酸化物と二硫化炭素を反応させて製造する。この場合特に残存アルカリ水酸化物が本発明の範囲内に収まる条件、即ち過剰のアルカリ水酸化物を減らして反応することによって製造できる。 Piperazine di-N, N′-biscarbodithioate is produced by reacting piperazine, an alkali hydroxide and carbon disulfide according to the method described in Patent Document 1 and others. In this case, it can be produced by reacting under the condition that the remaining alkali hydroxide falls within the scope of the present invention, that is, reducing the excess alkali hydroxide.
本発明の重金属処理剤中はアルカリ水酸化物を含有するが、アルカリ水酸化物としては、水酸化カリウム、水酸化ナトリウム、水酸化リチウムからなる群から選ばれる１種または２種以上の混合物が用いられる。 The heavy metal treating agent of the present invention contains an alkali hydroxide, and as the alkali hydroxide, one or a mixture of two or more selected from the group consisting of potassium hydroxide, sodium hydroxide and lithium hydroxide is used. Used.
本発明で用いられるアルカリ水酸化物の合計濃度は０．１１重量％以上０．３重量％未満である。０．３重量％以上の場合、−５℃度程度で結晶が析出し低温安定性は十分でなく、アルカリ水酸化物濃度が０．１１重量％未満、又は水酸化物イオン濃度が０．０８重量％未満の場合、二硫化炭素等の有害ガスの発生量が大きくなるため好ましく無い。 The total concentration of the alkali hydroxide used in the present invention is 0.11% by weight or more and less than 0.3% by weight. In the case of 0.3% by weight or more, crystals are precipitated at about −5 ° C. and the low temperature stability is not sufficient, the alkali hydroxide concentration is less than 0.11% by weight, or the hydroxide ion concentration is 0.08. When the amount is less than% by weight, the generation amount of harmful gas such as carbon disulfide is not preferable.
従来のピペラジンジチオカルバミン酸塩を主成分とする重金属処理剤においては、分解生成物である二硫化炭素等のガス発生抑制等の目的からアルカリ水酸化物濃度を０．３重量％以上とすることが通常であった。本発明の重金属処理剤はアルカリ水酸化物を水酸化カリウム、水酸化ナトリウム、水酸化リチウムからなる群から選ばれる１種または２種以上の混合物とし、アルカリ水酸化物濃度を０．３重量％未満とすることにより、低温安定性とガス発生の両方が著しく低くすることができる。 In the conventional heavy metal treating agent mainly composed of piperazine dithiocarbamate, the alkali hydroxide concentration may be 0.3% by weight or more for the purpose of suppressing the generation of gas such as carbon disulfide as a decomposition product. It was normal. In the heavy metal treating agent of the present invention, the alkali hydroxide is one or a mixture of two or more selected from the group consisting of potassium hydroxide, sodium hydroxide and lithium hydroxide, and the alkali hydroxide concentration is 0.3% by weight. By making it less than this, both low temperature stability and gas generation can be remarkably lowered.
本発明の重金属処理剤は、重金属汚染物質として飛灰、土壌、スラッジ等の処理に用いることができる。 The heavy metal treating agent of the present invention can be used for treating fly ash, soil, sludge and the like as heavy metal contaminants.
これらの重金属汚染物質中の重金属としては、鉛、カドミウム、クロム、水銀のいずれかを含有する物質が例示できる。 Examples of heavy metals in these heavy metal contaminants include substances containing any of lead, cadmium, chromium, and mercury.
本発明の重金属処理剤を用いた重金属処理方法は、特に限定されるものではなく、本発明の重金属処理剤と被処理物を十分に混合すればよい。重金属処理剤の使用量は重金属汚染物質の状態、重金属の含有量や重金属の形態により異なるが、通常、例えば飛灰に対しては０．０１〜３０重量％の範囲で使用される。また、処理を容易にするため、処理物に対して５〜５０重量％の加湿水を混練時に添加してもよい。 The heavy metal processing method using the heavy metal processing agent of the present invention is not particularly limited, and the heavy metal processing agent of the present invention and the object to be processed may be sufficiently mixed. The amount of heavy metal treating agent used varies depending on the state of heavy metal contaminants, the content of heavy metals and the form of heavy metals, but is usually used in the range of 0.01 to 30% by weight, for example, for fly ash. Moreover, in order to make a process easy, you may add 5-50 weight% humidified water with respect to a processed material at the time of kneading | mixing.
本発明の重金属処理剤は高濃度であるにもかかわらず特に低温安定性が高く、冬季、寒冷地においても結晶の析出がなく、安定して使用することができる。さらに少ない添加率で重金属の処理をすることができ、使用時の有害ガス発生量も少なく、安全に使用することができる。 Although the heavy metal treating agent of the present invention has a high concentration, the low temperature stability is particularly high, and it can be stably used without precipitation of crystals even in winter and cold regions. Furthermore, heavy metals can be processed with a small addition rate, and the amount of harmful gas generated during use is small, so that it can be used safely.
以下本発明を実施例で説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
実施例１
ピペラジン―Ｎ，Ｎ’―ビスカルボジチオ酸カリウムを４０重量％、水酸化リチウムを０．１５重量％、水酸化物イオンを０．１１重量％となるように純水に溶解させ、ピペラジン―Ｎ，Ｎ’―ビスカルボジチオ酸カリウムと水酸化リチウムの混合水溶液とした。当該水溶液６０ｇとα―アルミナ０．５μｍ（和光純薬工業株式会社）１０ｍｇ、回転子を１００ｍｌのガラス瓶に入れた。次に、それを恒温高湿槽ＬＨ４１−１３Ｐ（ナガノサイエンス株式会社）内に設置した冷媒の塩化カルシウム水溶液槽内に設置し、スターラーを用いて４００〜５００ｒｐｍで攪拌しながら、０℃から−８℃までの温度範囲を、−１℃／２４時間で冷却し、結晶が析出する温度を確認した。その結果を表１に示す。該溶液においては−８℃まで溶液中に結晶の析出は見られず、低温安定性に優れていた。
Example 1
Piperazine-N, N′-biscarbodithioate potassium is dissolved in pure water to 40% by weight, lithium hydroxide 0.15% by weight and hydroxide ion 0.11% by weight. , N′-biscarbodithioic acid potassium and lithium hydroxide mixed aqueous solution. The aqueous solution 60 g, α-alumina 0.5 μm (Wako Pure Chemical Industries, Ltd.) 10 mg, and the rotor were placed in a 100 ml glass bottle. Next, it is installed in a calcium chloride aqueous solution tank of a refrigerant installed in a constant temperature and high humidity tank LH41-13P (Nagano Science Co., Ltd.), and stirred at 400 to 500 rpm using a stirrer. The temperature range up to 0 ° C. was cooled at −1 ° C./24 hours, and the temperature at which crystals precipitated was confirmed. The results are shown in Table 1. In the solution, no precipitation of crystals was observed in the solution up to -8 ° C, and the low-temperature stability was excellent.
４０ｍｌのガラスバイアル瓶に該水溶液を３ｍｌ採り、２５℃で１日静置後のバイアル瓶内の気体の二硫化炭素濃度をガスクロマトグラフィーにより測定を行った。その結果を表１に示す。その濃度は１ｐｐｍ以下であり、ガス発生量が低いことが確認された。 3 ml of the aqueous solution was taken in a 40 ml glass vial, and the carbon disulfide concentration of the gas in the vial after standing at 25 ° C. for 1 day was measured by gas chromatography. The results are shown in Table 1. The concentration was 1 ppm or less, and it was confirmed that the amount of gas generated was low.
実施例２
ピペラジン―Ｎ，Ｎ’―ビスカルボジチオ酸カリウムを４０重量％、水酸化リチウムを０．２５重量％、水酸化物イオンを０．１８重量％とした以外は、実施例１と同様の操作を行った。その結果を表１に示す。
Example 2
The same operation as in Example 1 was carried out except that piperazine-N, N′-biscarbodithioate potassium was 40 wt%, lithium hydroxide was 0.25 wt%, and hydroxide ion was 0.18 wt%. went. The results are shown in Table 1.
−８℃においても結晶の析出が見られず、二硫化炭素の測定濃度は１ｐｐｍ以下であり、ガス発生量が低かった。 Crystal precipitation was not observed even at -8 ° C, the measured concentration of carbon disulfide was 1 ppm or less, and the amount of gas generated was low.
実施例３
ピペラジン―Ｎ，Ｎ’―ビスカルボジチオ酸カリウムを４０重量％、水酸化ナトリウムを０．２０重量％、水酸化物イオンを０．０９重量％とした以外は、実施例１と同様の操作を行った。その結果を表１に示す。
Example 3
The same operation as in Example 1 was conducted except that potassium piperazine-N, N′-biscarbodithioate was 40% by weight, sodium hydroxide was 0.20% by weight and hydroxide ion was 0.09% by weight. went. The results are shown in Table 1.
−８℃においても結晶の析出がなく、二硫化炭素濃度の測定濃度は１ｐｐｍ以下であり、ガス発生量が低かった。 Even at −8 ° C., no crystal was precipitated, and the measured carbon disulfide concentration was 1 ppm or less, and the amount of gas generated was low.
実施例４
ピペラジン―Ｎ，Ｎ’―ビスカルボジチオ酸カリウムを４０重量％、水酸化ナトリウムを０．２５重量％、水酸化物イオンを０．１１重量％とした以外は、実施例１と同様の操作を行った。その結果を表１に示す。結果を表１に示す。
Example 4
The same operation as in Example 1 was carried out except that piperazine-N, N′-biscarbodithioate potassium was 40 wt%, sodium hydroxide was 0.25 wt%, and hydroxide ion was 0.11 wt%. went. The results are shown in Table 1. The results are shown in Table 1.
−８℃においても結晶の析出がなく、二硫化炭素濃度の測定濃度は１ｐｐｍ以下であり、ガス発生量が低かった。 Even at −8 ° C., no crystal was precipitated, and the measured carbon disulfide concentration was 1 ppm or less, and the amount of gas generated was low.
実施例５
ピペラジン―Ｎ，Ｎ’―ビスカルボジチオ酸カリウムを４０重量％、水酸化カリウムを０．２７重量％、水酸化物イオンを０．０８重量％とした以外は、実施例１と同様の操作を行った。その結果を表１に示す。
Example 5
The same operation as in Example 1 was carried out except that piperazine-N, N′-biscarbodithioate potassium was 40 wt%, potassium hydroxide was 0.27 wt%, and hydroxide ion was 0.08 wt%. went. The results are shown in Table 1.
−８℃においても結晶の析出がなく、二硫化炭素濃度の測定濃度は１ｐｐｍ以下であり、ガス発生量が低かった。 Even at −8 ° C., no crystal was precipitated, and the measured carbon disulfide concentration was 1 ppm or less, and the amount of gas generated was low.
実施例６
ピペラジン―Ｎ，Ｎ’―ビスカルボジチオ酸カリウムを４０重量％、水酸化ナトリウムを０．２０重量％、水酸化カリウムを０．０５重量％、水酸化物イオンを０．１０重量％とした以外は、実施例１と同様の操作を行った。
Example 6
Except for piperazine-N, N′-biscarbodithioate potassium 40 wt%, sodium hydroxide 0.20 wt%, potassium hydroxide 0.05 wt% and hydroxide ion 0.10 wt% The same operation as in Example 1 was performed.
−８℃においても結晶の析出がなく、二硫化炭素濃度の測定濃度は１ｐｐｍ以下であり、ガス発生量が低かった。 Even at −8 ° C., no crystal was precipitated, and the measured carbon disulfide concentration was 1 ppm or less, and the amount of gas generated was low.
比較例１
ピペラジン―Ｎ，Ｎ’―ビスカルボジチオ酸カリウムを４０重量％、水酸化リチウムを０．１重量％、水酸化物イオンを０．０７重量％とした以外は、実施例１と同様の操作を行った。
Comparative Example 1
The same operation as in Example 1 was conducted except that potassium piperazine-N, N′-biscarbodithioate was 40% by weight, lithium hydroxide was 0.1% by weight and hydroxide ion was 0.07% by weight. went.
二硫化炭素濃度の測定濃度は１．３ｐｐｍであり、実施例に比べてガス発生量が高かった。 The measured concentration of carbon disulfide concentration was 1.3 ppm, and the amount of gas generated was higher than that in the examples.
比較例２
ピペラジン―Ｎ，Ｎ’―ビスカルボジチオ酸カリウムを４０重量％、水酸化リチウムを０．３重量％、水酸化物イオンを０．２１重量％とした以外は、実施例１と同様の操作を行った。その結果を表１に示す。
Comparative Example 2
The same operation as in Example 1 was carried out except that piperazine-N, N′-biscarbodithioate potassium was 40 wt%, lithium hydroxide was 0.3 wt%, and hydroxide ion was 0.21 wt%. went. The results are shown in Table 1.
−５℃において結晶の析出が確認され、実施例に比べて低温安定性に劣っていた。 Crystal precipitation was confirmed at −5 ° C., and the low temperature stability was inferior to that of the example.
比較例３
ピペラジン―Ｎ，Ｎ’―ビスカルボジチオ酸カリウムを４０重量％、水酸化ナトリウムを０．１５重量％、水酸化物イオンを０．０６重量％とした以外は実施例と同様の操作を行った。
Comparative Example 3
The same operation as in the example was performed except that potassium piperazine-N, N′-biscarbodithioate was 40 wt%, sodium hydroxide was 0.15 wt%, and hydroxide ions were 0.06 wt%. .
二硫化炭素濃度の測定濃度は１．７ｐｐｍであり、実施例に比べてガス発生量が高かった。 The measured concentration of the carbon disulfide concentration was 1.7 ppm, and the amount of gas generated was higher than in the examples.
比較例４
ピペラジン―Ｎ，Ｎ’―ビスカルボジチオ酸カリウムを４０重量％、水酸化ナトリウムを０．３重量％、水酸化物イオンを０．１３重量％とした以外は実施例１と同様の操作を行った。
Comparative Example 4
The same operation as in Example 1 was carried out except that piperazine-N, N′-biscarbodithioate potassium was 40 wt%, sodium hydroxide was 0.3 wt%, and hydroxide ions were 0.13 wt%. It was.
−６℃において結晶の析出が確認され、実施例に比べて低温安定性に劣っていた。 Crystal precipitation was confirmed at −6 ° C., and the low temperature stability was inferior to that of the example.
比較例５
ピペラジン―Ｎ，Ｎ’―ビスカルボジチオ酸カリウムを４０重量％、水酸化カリウムを０．３重量％、水酸化物イオンを０．０９重量％とした以外は実施例と同様の操作を行った。
Comparative Example 5
The same operation as in the example was performed except that piperazine-N, N′-biscarbodithioate potassium was 40 wt%, potassium hydroxide was 0.3 wt%, and hydroxide ion was 0.09 wt%. .
−６℃において結晶の析出が確認され、実施例に比べて低温安定性に劣っていた。 Crystal precipitation was confirmed at −6 ° C., and the low temperature stability was inferior to that of the example.
比較例６
ピペラジン―Ｎ，Ｎ’―ビスカルボジチオ酸カリウムを４０重量％、水酸化ナトリウムを０．２５重量％、水酸化カリウムを０．０５重量％水酸化物イオンを０．１２重量％とした以外は実施例と同様の操作を行った。
Comparative Example 6
Except for piperazine-N, N′-biscarbodithioate potassium 40 wt%, sodium hydroxide 0.25 wt%, potassium hydroxide 0.05 wt% hydroxide ion 0.12 wt% The same operation as in the example was performed.
−６℃において結晶の析出が確認され、実施例に比べて低温安定性に劣っていた。 Crystal precipitation was confirmed at −6 ° C., and the low temperature stability was inferior to that of the example.
本発明の重金属処理剤は、低温時に結晶析出が起こりにくく、かつ、ガス発生量も少ないために、特に寒冷地での重金属処理に有効である。
The heavy metal treatment agent of the present invention is particularly effective for heavy metal treatment in cold regions because crystal precipitation hardly occurs at low temperatures and the amount of gas generation is small.
Claims (7)
The method for treating heavy metal contaminants according to claim 5, wherein the heavy metal contaminant is a substance containing any of lead, cadmium, chromium, and mercury.
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| CN102216410A (en) * | 2008-11-18 | 2011-10-12 | 东曹株式会社 | Solid heavy metal processing agent, method for producing same and use of same |
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